US6537425B2

US6537425B2 - Process for loading fibers with calcium carbonate

Info

Publication number: US6537425B2
Application number: US09/903,003
Authority: US
Inventors: Jörg Rheims; Klaus Doelle; Oliver Heise; Werner Witek
Original assignee: Voith Paper Patent GmbH
Current assignee: Voith Patent GmbH
Priority date: 2000-07-13
Filing date: 2001-07-11
Publication date: 2003-03-25
Anticipated expiration: 2021-07-11
Also published as: CA2352885A1; ATE275661T1; DE50103512D1; EP1172478A1; JP2002030592A; EP1172478B1; DE10033979A1; US20020026989A1

Abstract

During the chemical process of loading with calcium carbonate fibers contained in a pulp suspension, a medium containing calcium oxide or calcium hydroxide is added to the pulp suspension. This treated pulp suspension is charged in at least one reactor with pure carbon dioxide (or a medium containing carbon dioxide), which, during the progression of the reaction, converts at least a significant portion of the starting materials (calcium oxide and/or calcium hydroxide and carbon dioxide) into the reaction products, calcium carbonate and water. This reaction is accomplished by properly controlling the pulp suspension's pH.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention involves the loading of calcium carbonate into fibers contained in a pulp suspension.

2. Description of the Related Art

Pulp suspensions are used especially in paper and cardboard manufacture. The sparing use of raw material resources, due especially to economical and ecological concerns, is reflected in the paper production industry by the use of paper webs with lower basis weights, as well as by the partial replacement of pulp with filling materials. If lower cost raw materials are used, the paper quality should at least be maintained. Among other things, the end product's strength, visual characteristics, and processability play key roles in this challenge.

SUMMARY OF THE INVENTION

The present invention relates to the further optimization of the paper production process, especially with regard to achieving the greatest possible profitability and the highest possible pulp suspension quality.

The invention, in one form thereof, comprises a process of adding to the pulp suspension a medium containing calcium oxide and/or calcium hydroxide. The pulp suspension subjected to this treatment is additionally charged in at least one reactor with pure carbon dioxide or a medium containing carbon dioxide. During the course of the chemical reaction, at least a significant portion of the above-mentioned starting materials (calcium oxide and/or calcium hydroxide and carbon dioxide) is converted into the reaction products of calcium carbonate and water. This conversion is achieved by accordingly controlling the pulp suspension's pH.

The pH can be measured at one or several locations during execution of the process. The pulp suspension is further characterized by a material density (i.e., consistency) greater than 5%, and preferably between 15% and 40%. The density is also controllable within this range.

The addition of a medium containing calcium oxide and/or calcium hydroxide results in an exothermic reaction. Liquid calcium hydroxide (lime milk) is preferable for this application. That the reaction is exothermic in nature means that the water settled in or on the pulp suspension's fibrous material is not necessarily required to start and continue the chemical reaction. Significantly greater profitability and higher quality pulp suspension are achieved as a result of this reaction.

During loading of the fibers, calcium carbonate is deposited onto the wetted fiber surfaces through the addition of calcium oxide and/or calcium hydroxide to the moist fibrous material, whereby at least a portion of this calcium compound can associate with the water in the fibrous material. After this treatment, the fibrous material is charged with the pure carbon dioxide or with the medium containing carbon dioxide. Moreover, the CaCO₃that is formed can create a suspension around the fibers. Accordingly, the fibers are loaded with the filling material calcium carbonate, whereby deposition onto the wetted fibrous surfaces is performed according to a so-called “Fiber Loading™ Process”, as described in document U.S. Pat. No. 5,223,090. During this “Fiber Loading™ Process”, Co₂reacts with calcium hydroxide to form water and calcium carbonate.

The term “wetted fiber surface” can include the wetted surfaces of all individual fibers. This applies especially to cases where the fibers are loaded with calcium carbonate on their external as well as on their inner surfaces (lumen).

A preferred version of the invention process compares the respective pH value with a corresponding preset value and minimizes or eliminates the control deviation through manipulation of at least one of the following process variables:

Length of time pulp suspension remains in the reactor;

Pulp suspension feed rate;

Carbon dioxide pressure;

Temperature of the pulp suspension and/or the calcium compound;

Pressure inside the reactor;

Temperature of the CO₂;

Pressure of the CO₂;

Concentration of CO₂in the medium;

Concentration of the CaO, the Ca(OH)₂, and the fibers; and

Specific fiber surface area.

It is advantageous to maintain control of the pulp suspension pH within a range of about 5.5 to 10.5.

It is also advantageous when the pulp suspension's ash content is controllable within a range of about 1% to about 70%.

It is preferable to feed the carbon dioxide in a gaseous state. Further, the temperature of the fed carbon dioxide can be adjusted or controlled within a range of about 10° C. to about 250° C.

In certain cases, it is also advantageous to use other visual characteristics such as brightness, light scattering properties, opacity, color location, and the light dispersion coefficient as indicators of the status of the chemical reaction.

The pH should be measured during at least one of the following steps: at least before and after the reaction; during the reaction; and possibly multiple measurements throughout (optional).

It is preferable to measure the pH at the end of the chemical reaction or following the enlargement of the specific surface area, such enlargement being achieved by using as least one fluffer.

The pressure can be controlled within the range of about 0.1 to about 20 bar.

Furthermore, the pulp suspension is subjected to shearing force, preferably in at least one fluffer, in order to enlarge its specific surface area, among other things.

Furthermore, loading the fibers with calcium carbonate can be accomplished as described in document U.S. Pat. No. 5,223,090, the contents of which are hereby incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:

FIG. 1 is a schematic drawing of an apparatus for loading with calcium carbonate fibers contained in a pulp suspension;

FIGS. 1a-1 c illustrate various pH curves over the reaction time during a loading process; and

FIG. 2 is a schematic drawing of another embodiment of an apparatus for loading fibers.

Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate one preferred embodiment of the invention, in one form, and such exemplifications are not to be construed as limiting the scope of the invention in any manner.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 is a schematic depiction of an exemplary apparatus 10 for loading with calcium carbonate (CaCO₃) fibers contained in a pulp suspension. Accordingly, apparatus 10 serves to deposit calcium carbonate onto the wetted fibrous surfaces of the fiber material. In principle, loading of the fibers can be accomplished according to the previously-mentioned “Fiber Loading™ Process.

Apparatus

10 can include one or several reactors 12 _x, in which the pulp suspension (loaded with calcium oxide (CaO) and/or calcium hydroxide (Ca(OH)₂) can be charged with pure carbon dioxide (CO₂) or with a medium containing carbon dioxide (CO₂).

One fluffer 14 can be provisioned before and/or after and/or in each of reactor or reactors 12 _xin which the pulp suspension's fibrous material is split with the goal of enlarging the fibrous material's specific surface area in order to optimize access for the reaction products to the fibrous material surface. This surface area enlargement further improves homogenization, and the “Fiber Loading™” process is accordingly optimized.

This surface area enlargement can occur by subjecting the pulp suspension to shearing forces (in a fluffer, for example). The pH measurement location can be at least before and after the reaction; during the reaction; and/or, optionally, at multiple measurement sites throughout the process. The pH measurement is performed preferably at the end of the reaction after enlargement of the specific surface area of the fibers.

In the following example, furst fluffer 14 is placed between refiner 16 and reactor(s) 12 _x. Alternatively or additionally, fluffer 14 may be placed between at least one reactor 12 _xand tank 18. In the given example, another refiner 20 follows tank 18, which is followed by a paper machine PM.

Additional information contained in FIG. 1 is intended to serve strictly as an example and can be used individually or in a desired combination.

Apparatus

10 can therefore be used to achieve deposition of calcium carbonate onto the wetted fibrous surface of the fiber material, whereby this loading of fiber can proceed according to the previously mentioned “Fiber Loading™” process.

During the process, the medium containing calcium oxide and/or calcium hydroxide (slaked lime) can be added to the fibrous material in such a way that at least a portion of the medium can associate with the water present between the fibers, in the hollow fibers, and in their walls, resulting in the following chemical reaction:

The fibrous material is then charged in the appropriate reactor with carbon dioxide (CO₂) in such a way that calcium carbonate (CaCO₃) is deposited as widely as possible onto the wetted fibrous surfaces. This is represented by the following chemical reaction:

Using apparatus 10, the “Fiber Loading” process continues by adding a medium containing calcium oxide and/or calcium hydroxide to the pulp suspension. This pulp suspension is charged with a pure carbon dioxide medium or a medium containing carbon dioxide and during the chemical reaction at least a significant portion of the starting products, calcium oxide and/or calcium hydroxide and carbon dioxide, are converted to the reaction products calcium carbonate and water. This is accomplished by appropriately controlling the pH.

It is thereby advantageous to compare the current pH to an appropriate pH set value and to minimize or eliminate the deviation between these values by using at least one of the following variables:

Length of time pulp suspension remains in reactor 12 _x;

Pulp suspension feed rate,

Pressure of the carbon dioxide;

Temperature of the pulp suspension and/or the calcium hydroxide,

Pressure in reactor 12 _x;

Temperature of the CO₂;

Pressure of the CO₂;

Concentration of the CO₂in the medium;

Concentration of the CaO, the Ca(OH)₂, and the fibers; and

Specific surface area of the pulp fibers.

In FIGS. 1a-1 c, the pH values for various examples are depicted throughout respective reaction times.

Control of pH is also possible with the alternate apparatus design shown in FIG. 2. According to FIG. 2, pulp-starting material 22 is processed in a pulper 24 into a fibrous material 26 in which the fibers are already isolated (i.e., separated from each other) to at least a significant degree. Fibrous material 26 contains at least some water, which may be present between the fibers, in the internal spaces (lumen) and in the walls of the hollow fibers. Fibrous material 26 may also take the form of a so-called “dewatered crump pulp,” for example (e.g., U.S. Pat. No. 5,223,090).

Fibrous material 26 is finally fed into a collection container 28 or other similar vessel. A calcium-rich medium 30 containing calcium oxide and/or calcium hydroxide (slaked lime) is also added to collection container 28 so that a portion of this associates with the water present in the fibrous material (between the fibers, in the hollow fibers, and in their walls). The following and previously mentioned chemical reaction begins:

Immediately following the reaction, the fibrous material's dry content can be increased by feeding it through a press 32, whose power water 34, for example, is led back into the closed loop. In reactor 36, which is isolated by two fluffers 14, fibrous material 26 is charged with pure carbon dioxide or a medium containing carbon dioxide, as schematically indicated in FIG. 2 with the labeled arrow pointing into reactor 36. Upon being charged, fibrous material 26 is released through valve 38 to paper machine 40.

The charging of the fibrous material (previously processed as described above) with pure carbon dioxide or a medium containing carbon dioxide starts the following, previously-mentioned chemical reaction:

Regardless of the type of apparatus used, the following measures or characteristics, whether implemented individually or in combination with each other, are advantageous with regards to further optimization of the “Fiber Loading™” process.

The pulp suspension's pH can be measured for the purpose of monitoring and/or controlling the chemical reaction. It is preferable for the pH to be variable within a range of about 5.5 to about 10.5.

The pulp suspension's ash content is variable within a range from about 1% to about 70%.

Carbon dioxide is preferably added in a gaseous state. The temperature of the added carbon dioxide is variable within a range of about −10° C. to about 250° C.

Visual characteristics, such as brightness, light scattering properties, opacity, color location, and the light diffusion coefficient may be employed as indicators for control of the chemical reaction.

While controlling the chemical reaction, it is fundamentally possible to also employ pH, ash content and/or the proportion of calcium carbonate (CaCO₃) as variables.

In the areas of FIG. 1 labeled with “VD”, dilution (with H₂O) is also possible.

The following measures or characteristics, whether employed individually or in a desired combination, can promote further optimization of the Fiber Loading™ process:

Addition of pulp:

Volume and mass flow rate are controllable;

Temperature is controllable within a range of about 5° C. to about 95° C.;

Material density is controllable within a range of about 15% to about

40%, preferably from about 20% to about 25%; and

pH is controllable from about 10 to about 13;

Calcium carbonate (CaCO) in the reactor:

Crystal types: rhombohedral, scalar, rosette, spherical, needle-shaped, prism-shaped, aragonitic, flat shaped, GCC, and other similar crystalline forms;

Reaction under pressure (about 0.1 to about 20 bar);

Temperature from about −10° C. to about 200° C.; and

Dwell time from about 1 minute to about 1 hour;

Fluffing:

Enlarges the specific surface area;

Can be employed before, after and/or in a reactor or reactors;

Have a dissociation width from about 0.1 to about 100 mm, such a width preferably being adjustable;

Permit addition of energy within a range of about 5 kWh/t to about 200 kWh/t;

Refining:

Before, after, in a reactor or reactors, and/or during the “Fiber Loading™” process;

Pressure vessel or reactor (*)/dwell pulper after reactor (**):

(*) Crystal types: rhombohedral, scalar, rosette, spherical, needle-shaped, prism-shaped, aragonitic, plate-shaped, GCC, and other similar crystalline forms;

(*) Reaction under about 0.1 bar to about 20 bar pressure;

(**) Temperature within the range of about −10° C. to about 250° C.;

(*) pH adjustable from about 5.5 to about 10.5;

(**) Material density of about 0.1% to about 15%;

(**) Addition of CO₂; and

(**) Dwell time; and

CaCO₃proportion of the pulp:

With an underlying percentage by mass of about 1% to about 70% of the filling material, about 1% to about 60% filling material being deposited onto the fibers and the remaining being free FLPCC™ (Fiber Loaded Precipitated Calcium Carbonate) in the suspension.

While this invention has been described as having a preferred design, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.

Claims

What is claimed is:

1. A chemical process of loading calcium carbonate into fibers, the fiber being contained in a pulp suspension, said chemical process comprising the steps of:

providing a pulp suspension of greater than five percent (5%) consistency and a calcium-rich medium, said calcium-rich medium containing at least one of calcium oxide and calcium hydroxide;

adding said calcium-rich medium to said pulp suspension to form a calcium-rich pulp suspension;

providing at least one reactor, each reactor having a source of a carbon-dioxide medium connected thereto, said carbon-dioxide medium being comprised of one of pure carbon dioxide and a medium containing carbon dioxide, said carbon-dioxide medium having a medium temperature associated therewith, said medium temperature being at least one of adjustable and controllable within an approximate range of −10° C. to 250° C.;

charging said calcium-rich pulp suspension and said carbon-dioxide medium into said at least one reactor, said calcium-rich pulp suspension and said carbon-dioxide medium thereby causing a chemical reaction in a carbon dioxide rich atmosphere to form calcium carbonate and water; and

controlling a pH of at least one of said pulp suspension and said calcium-rich pulp suspension.

2. The chemical process of claim 1, further comprising the steps of:

measuring an actual pH of said at least one of said pulp suspension and said calcium-rich pulp suspension;

comparing the actual pH with a respective set point and determining an amount of deviation therebetween; and

one of minimizing and eliminating said amount of deviation between the actual pH and the respective set point through use of at least one of the following variables:

length of time said calcium-rich pulp suspension remains in each said reactor;

feed rate of at least one of said pulp suspension and said calcium-rich pulp suspension;

pressure of the carbon-dioxide medium;

temperature of at least one of said pulp suspension, said calcium-rich pulp suspension and said calcium-rich medium;

pressure inside each said reactor;

temperature of said carbon-dioxide medium;

concentration of carbon dioxide in said carbon-dioxide medium;

concentration of at least one of said calcium-rich medium and said fibers; and

specific surface area of said fibers.

3. The chemical process of claim 1, wherein the pH of at least one of said pulp suspension and said calcium-rich pulp suspension is controllable within a range of about 5.5 to about 10.5.

4. The chemical process of claim 1, wherein each of said pulp suspension and said calcium-rich pulp suspension have an ash content associated therewith, said ash content of at least one of said pulp suspension and said calcium-rich pulp suspension being controllable within a range of about 1% to about 70%.

5. The chemical process of claim 1, wherein said carbon-dioxide medium is added in a gaseous state.

6. The chemical process of claim 1, wherein the pH of said at least one of said pulp suspension and said calcium-rich pulp suspension is measured at least one of before, during and after the chemical reaction.

7. The chemical process of claim 1, wherein the pH of said at least one of said pulp suspension and said calcium-rich pulp suspension is measured at multiple intervals throughout the chemical process.

8. The chemical process of claim 1, wherein the pH of said calcium-rich pulp suspension is measured at the end of the chemical reaction.

9. The chemical process of claim 1, wherein pressure inside each said reactor is controlled within a range of about 0.1 bar to about 20 bar.

10. The chemical process of claim 1, comprising the further step of subjecting at least one of said pulp suspension and said calcium-rich pulp suspension to shearing forces.

11. The chemical process of claim 10, wherein each said reactor has at least one fluffer associated therewith, said shearing forces being provided by said at least one fluffer.

12. A chemical process of loading calcium carbonate into fibers, the fibers being contained in a pulp suspension, comprising the steps of:

providing at least one reactor, each reactor having a source of a carbon-dioxide medium connected thereto, said carbon-dioxide medium being comprised of one of pure carbon dioxide and a medium containing carbon dioxide;

charging said calcium-rich pulp suspension and said carbon-dioxide medium into said at least one reactor, said calcium-rich pulp suspension and said carbon-dioxide medium thereby causing a chemical reaction in a carbon dioxide rich atmosphere to form calcium carbonate and water;

controlling a pH of at least one of said pulp suspension and said calcium-rich pulp suspension; and

using at least one visual characteristic of said calcium-rich pulp suspension in said reactor as an indicator for the progression of the chemical reaction in each said reactor, each said visual characteristic being one of brightness, light scattering properties, opacity, color and light dispersion coefficient.

13. A chemical process of loading calcium carbonate into fibers, the fibers being contained in a pulp suspension, comprising the steps of:

providing at least one fluffer in association with said at least one reactor;

using said at least one fluffer to enlarge a specific surface area of said fibers;

measuring a pH of at least one of said pulp suspension and said calcium-rich pulp supension upon enlarging the specfic surface area of said fibers; and

controlling said pH of at least one of said pulp suspension and said calcium-rich pulp suspension.